Earth abundant, first row transition metals have distinct electronic structures from second and their row transition elements traditionally used in catalysis. The presence of kinetically and thermodynamically one electron differentiated redox states offers both an opportunity and challenge. Rational control of redox properties offers an opportunity for new catalytic reactivity. Our group has explored redox-active ligands, those that engage in reversible one-electron redox changes, with a transition metal as well as more traditional electron rich donors that tend to favor two electron redox events at the metal. Importantly, this approach to electronic structure has proven to be an important design principle for tailoring catalytic reactivity.
Radical Ligands Confer Nobility of Base-Metal Catalysts
Paul J. Chirik and Karl Wieghardt
Science 2010, 327, 794-795.
Preface: Forum on Redox-Active Ligands
Paul J. Chirik
Inorg. Chem. 2011, 50, 9737-9740.